CN103569491B - The cover piece for preventing content from adhering to - Google Patents

The cover piece for preventing content from adhering to Download PDF

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Publication number
CN103569491B
CN103569491B CN201310332056.2A CN201310332056A CN103569491B CN 103569491 B CN103569491 B CN 103569491B CN 201310332056 A CN201310332056 A CN 201310332056A CN 103569491 B CN103569491 B CN 103569491B
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Prior art keywords
layer
heat
cover piece
silicon dioxide
sealing
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CN103569491A (en
Inventor
羽野隆之
唐津诚
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Lishennoco Packaging Co.,Ltd.
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Showa Denko Packaging Co Ltd
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Priority claimed from JP2012171378A external-priority patent/JP2014031179A/en
Priority claimed from JP2012171372A external-priority patent/JP6072459B2/en
Application filed by Showa Denko Packaging Co Ltd filed Critical Showa Denko Packaging Co Ltd
Publication of CN103569491A publication Critical patent/CN103569491A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D53/00—Sealing or packing elements; Sealings formed by liquid or plastics material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D77/00—Packages formed by enclosing articles or materials in preformed containers, e.g. boxes, cartons, sacks or bags
    • B65D77/10—Container closures formed after filling
    • B65D77/20—Container closures formed after filling by applying separate lids or covers, i.e. flexible membrane or foil-like covers

Abstract

The present invention provides a kind of cover piece for preventing content from adhering to.It is being laminated in substrate layer（1）Heat-sealing seal layer（5）Outer surface, form anti-adhesion layer using following wet silicon dioxide particles（6）, the wet silicon dioxide particle is that more than viscosity 100cst polysiloxanes, particularly dimethyl polysiloxane are used as into inorganic agent and carried out the hydrophobicity wet silicon dioxide particle of silicic acid anhydride.Or it is being laminated in substrate layer（1）Heat-sealing seal layer（5）Outer surface, form anti-adhesion layer using following wet silicon dioxide particles（6）, the wet silicon dioxide particle be hydrophobic processing be di-n-butyl amine sorption amount（DBA adsorbances）For below 200mmol/kg hydrophobicity wet silicon dioxide particle.The cover piece for preventing content attachment of this spline structure, can maintain heat sealability, sealing well, and effectively prevent the content of Yoghourt etc. to be attached to the back side of lid.

Description

The cover piece for preventing content from adhering to
Technical field
The present invention relates to the heat-sealing cover piece for the container for packing for being mainly used in foodstuff, more particularly, it is related to application In Yoghourt, fruit jelly, pudding, jam, coffee with milk（Caffellatte）Deng the cup-like containers being packed for there is anti-content The cover piece of thing tack.
Background technology
The heat-sealing of this kind is sealed（Heat-seal）Cover piece（Gai Cai）, it is generally formed as in the lamination structure by base material film and aluminium foil Into substrate layer aluminium foil surface side, as needed across middle resin layer and there is provided heat sealing agent, i.e. heat-sealing to seal layer（Heat-seal Layer）Cover piece, it covers above the container body of the cup-shaped for the packed article for being filled with Yoghourt etc. and is open, by by peripheral part Heat fused is on the upper limb flange part of container body, to form hermetically sealed package.
Therefore, such cover piece, it is being required good heat sealability, sealing and for the appropriate easily peelable of Kaifeng Property while, it is desirable to have content non-tack, can prevent content be attached to the inner face side of container cover piece carry on the back Face（The inside）.If content is attached to the back side of cover piece, has at Kaifeng and make finger, clothes or the anxiety on periphery dirty, and Produce and wasted by abandoning for content caused by damage, or spend the man-hour for stripping attachment, and produce and cause unclean sense etc. It is unfavorable.
For such requirement, in the past on possessing the cover piece of anti-content adhesion property, it is proposed that such as following patents Such motion shown in document 1,2.
First technology shown in patent document 1, it is the outer surface that layer is sealed in heat-sealing, as anti-content adhesion layer, is formed The porous layer of the tridimensional network formed by the hydrophobic oxide particulate of fine hydrophobic silica etc..
The first motion technology of the patent document 1, although excellent effect can be obtained in terms of content adhesion effect is prevented Fruit, but the heat endurance of anti-adhesion layer（Heat resistance）Difference, in the case where being subjected to bad hot resume, having prevents attachment from imitating The easy damaged difficult point of fruit.That is, as hydrophobic oxide particulate, use using by the silicon dioxide microparticle that dry process manufactures as The primary particle average grain diameter of typical example is hydrophobic oxide particulate ultra tiny as 3~100nm, and being particularly should In the case of the formation that the anti-content adhesion layer of the cover piece of layer is sealed for the heat-sealing with general hot melt type, anti-adhesion During drying after the particle dispersion liquid coating in the formation process of layer, if heating-up temperature is high or drying time is elongated, prevent in Tolerant adhesion effect is significantly impaired, it is possible to can not maintain stable anti-adhesion performance.Therefore, there is work during cover piece manufacture Sequence management becomes somewhat troublesome difficult point.
The problem of such heat resistance, it is believed that caused by being following reason：Heat when because drying or when being sealed in heat-sealing It is standby in the radiant heat from thermal station, heat-sealing seals the hotmelt of layer（Hot-melt adhesive：heat melt adhesive） During melting, fine oxide fine particle is sunk in hotmelt, or, the molten component of hotmelt is showed by capillary As and the gap that enters between particulate, between filling particle, lower the hydrophobic of hydrophobic silica（Drying;Water repellent）Property surface Product, thus can not fully obtain preventing content adhesion effect.
On the other hand, for the particularly heat endurance of the first technology of patent document 1 as described above the problem of, as Seek to solve the problem and be able to ensure that the improving environment of excellent non-tack, the present inventor has been previously proposed patent document Invention described in 2.
The improvement motion technology, it is mainly characterized by：As the formation material of anti-adhesion layer, instead of known hydrophobic The use of property dry type silica, uses hydrophobic wet silicon dioxide particle.Its general particle diameter of wet silicon dioxide particle It is more much larger than dry type silica particle for micron-scale.Therefore, sealed in heat-sealing in the case that layer is made up of hotmelt, Even if the adhesive melts, hydrophobic silica particles, which are also difficult to sink to heat-sealing, to be sealed in layer.Therefore, easily remain anti-well The hydrophobicity on the surface of adhesion layer.Thus, compared to the first technology of patent document 1, the influence of heat can be improved.
But on the other hand, due to wet silicon dioxide particle, its particle diameter is bigger, therefore with using by ultra tiny one The situation for the dry type silica particle that the agglomerate of secondary particle is formed is compared, with coating weight（Adhesion amount）Relativeness in Surface hydrophobicity is poor, in order to obtain the coating that high anti-adhesion performance needs the hydrophobicity wet silicon dioxide of slightly more amounts, because This, also seals the adherence of layer relative to heat-sealing（It is closely sealed；Adhesion）The difficult point that property is easily deteriorated, in order to practical, it is strongly required this The further improvement of a little aspects.
Patent document 1：No. 4348401 publications of Japanese Patent No.
Patent document 2：No. 4668352 publications of Japanese Patent No.
The content of the invention
The invention that the present invention is corresponding to requirement as described above of the prior art and completed, specifically, its purpose It is to provide following improving environments：Even if with thermally influenced, the good of sufficient anti-content adhesion property is also able to maintain that Heat resistance, even and the coating weight of few wet silicon dioxide particulate can also ensure that high anti-content tack Can, and can ensure that hydrophobicity wet silicon dioxide particle phase seals the adherence of layer for heat-sealing well, it can ensure above-mentioned anti- The only stable continuation of content adhesion effect.
The present inventor is diligently tested repeatedly under above-mentioned purpose and the result of research, finds：According to above-mentioned patent document 2 First technology, it is the layer that is formed by hydrophobicity wet silicon dioxide to make anti-adhesion layer, also, by using the hydrophobicity is wet Formula silica has especially carried out the hydrophobicity wet silicon dioxide particle of silicic acid anhydride with specific inorganic agent, used The wet silicon dioxide particle of the polysiloxane hydrophobic in particular viscosity region（1st invention）, or, by using especially high Spend the hydrophobicity wet silicon dioxide particle with high hydrophobic rate more than setting of ground silicic acid anhydride（2nd hair It is bright）, can extremely efficient solve above-mentioned problem, so that completing the present invention.
That is, it is of the invention, as its feature item, propose following schemes.
［ 1 ］ a kind of cover piece for preventing content from adhering to, it is at least there is substrate layer and heat-sealing to seal layer, and layer is sealed in the heat-sealing Outer surface be provided with anti-adhesion layer heat-sealing cover piece, it is characterised in that above-mentioned anti-adhesion layer by use more than viscosity 100cst The hydrophobicity wet silicon dioxide particle that polysiloxanes has carried out silicic acid anhydride is formed.
［ 2 ］ a kind of cover piece for preventing content from adhering to, it is at least there is substrate layer and heat-sealing to seal layer, and layer is sealed in the heat-sealing Outer surface be provided with the heat-sealing cover piece of anti-adhesion layer, it is characterised in that above-mentioned anti-adhesion layer is by di-n-butyl amine adsorbance Below 200mmol/kg hydrophobicity wet silicon dioxide particle is formed.
［ 3 ］ cover piece for preventing content attachment according to preceding paragraph 1, the two of above-mentioned hydrophobicity wet silicon dioxide particle N-butylamine adsorbance is below 200mmol/kg.
［ 4 ］ cover piece for preventing content attachment according to preceding paragraph 1 or 3, the above-mentioned poly- silicon for silicic acid anhydride agent The viscosity of oxygen alkane is below 2000cst.
［ 5 ］ cover piece for preventing content attachment according to preceding paragraph 1,3 or 4, for the above-mentioned poly- of silicic acid anhydride agent Siloxanes is dimethyl polysiloxane.
［ 6 ］ cover piece for preventing content attachment according to preceding paragraph 2 or 3, above-mentioned hydrophobicity wet silicon dioxide particle Di-n-butyl amine adsorbance be 30~100mmol/kg.
［ 7 ］ cover piece that content adheres to, dredging in above-mentioned anti-adhesion layer are prevented according to any one of preceding paragraph 1~6 The coating weight of water-based wet silicon dioxide particle, 0.1~1.0g/m is calculated as with weight after drying2。
［ 8 ］ cover piece for preventing content attachment according to any one of preceding paragraph 1~7, above-mentioned hydrophobicity wet type dioxy The average grain diameter of SiClx particle is 0.5~7.0 μm.
［ 9 ］ according to any one of preceding paragraph 1~8 prevent content adhere to cover piece, above-mentioned heat-sealing seal layer by containing Ethene-beta-unsaturated esters copolymer, wax and tackifier are formed as the resin combination of required composition, above-mentioned resin combination it is soft It is more than 90 DEG C to change point, and the fusing point of above-mentioned wax is more than 80 DEG C.
［ 10 ］ cover piece for preventing content attachment according to preceding paragraph 9, the softening point of above-mentioned resin combination is 100 DEG C More than, and the fusing point of above-mentioned wax is more than 90 DEG C.
［ 11 ］ cover piece for preventing content attachment according to preceding paragraph 9 or 10, above-mentioned ethene-beta-unsaturated esters copolymer Fusing point is 70~100 DEG C.
［ 12 ］ cover piece for preventing content attachment according to any one of preceding paragraph 1~8,
Above-mentioned heat-sealing seals layer by containing resin group of ethene-beta-unsaturated esters copolymer, wax and the tackifier as required composition Compound is formed,
The fusing point of above-mentioned ethene-beta-unsaturated esters copolymer is 70~100 DEG C,
The fusing point of above-mentioned wax is 80~130 DEG C,
The softening point of above-mentioned resin combination is set to 90~160 DEG C.
［ 13 ］ cover piece for preventing content attachment according to any one of preceding paragraph 9~12, it is characterised in that above-mentioned tree It is 30~50 weight % that oil/fat composition, which has above-mentioned ethene-beta-unsaturated esters copolymer, wax is 30~50 weight %, tackifier be 5~ 25 weight % composition.
［ 14 ］ cover piece for preventing content attachment according to any one of preceding paragraph 1~13, above-mentioned hydrophobicity wet type two The oil absorption of silicon oxide particle is more than 50ml/100g.
［ 15 ］ cover piece for preventing content attachment according to any one of preceding paragraph 1~14, above-mentioned heat-sealing seal layer by soft Change more than 90 DEG C of point, the resin combination that the melt viscosity at 160 DEG C is below 4000mPas is formed.
［ 16 ］ cover piece for preventing content attachment according to any one of preceding paragraph 1~8,
Above-mentioned heat-sealing seals layer by containing resin group of ethene-beta-unsaturated esters copolymer, wax and the tackifier as required composition Compound is formed,
The fusing point of above-mentioned ethene-beta-unsaturated esters copolymer is 70~100 DEG C,
The softening point or fusing point of above-mentioned wax and tackifier are 80~130 DEG C,
The softening point of above-mentioned resin combination is 90~160 DEG C, melt viscosity at 160 DEG C for 2000~ 4000mPa·s。
［ 17 ］ cover piece for preventing content attachment according to any one of preceding paragraph 1~8,
Above-mentioned heat-sealing seals layer by containing the tree of acid modified polyolefin system resin and wax and/or tackifier as required composition Oil/fat composition is formed,
The fusing point of above-mentioned wax and tackifier is all more than 80 DEG C.
［ 18 ］ cover piece for preventing content attachment according to any one of preceding paragraph 1~17,
The outer surface of layer is sealed in above-mentioned heat-sealing, it is throughout entire surface close to be provided with the multiple small prominent of less than 100 μm of height Rise,
In the above-mentioned outer surface with the projection, formed with above-mentioned anti-adhesion layer,
Above-mentioned anti-adhesion layer, its adhesion amount are set to 0.05g/m2At most cover above and somewhat above-mentioned microspike Top end face amount below.
［ 19 ］ cover piece for preventing content attachment according to any one of preceding paragraph 1~18, above-mentioned anti-adhesion layer side The confficient of static friction on surface is set to less than 0.65.
Invented in ［ 1 ］（1st invention）In, the formation of the anti-adhesion layer on layer is sealed in heat-sealing, has used particle diameter is bigger to dredge Water-based wet silicon dioxide particle.Therefore, sealed in heat-sealing in the case that layer formed by hotmelt, even if the adhesive melts Melt, because compared with using the situation of ultra tiny dry type silica, particle diameter is big, therefore above-mentioned particle is also difficult to sink to heat-sealing Seal in layer, that does not reduce its surface significantly exposes area.And then it can effectively prevent the anti-adhesion property caused by heat affecting The reduction of energy.Although this is same with the first technology shown in above-mentioned patent document 2, in the present invention, and then as above-mentioned Hydrophobicity wet silicon dioxide particle, use and especially carried out with more than viscosity 100cts polysiloxane hydrophobic inorganic agent The hydrophobic silica particles of silicic acid anhydride.Such hydrophobic silica particles, pole is presented on its own surface High hydrophobicity, therefore the anti-adhesion layer formed by the hydrophobicity wet silicon dioxide, in fewer silicon dioxide granule Under coating weight, excellent anti-adhesion performance is given full play to.It is additionally, since and uses few coating weight i.e. enough, therefore can be good Ground keeps silicon dioxide granule to seal stationarity, the adherence of layer relative to heat-sealing, can avoid the dioxy caused by adhesion force deficiency The coming off of SiClx particle, peel off it is caused through when performance reduce, it is unhygienic.
It is not necessarily clear and definite that the mechanism of such effect can be obtained, but can be estimated as follows.Originally, hydrophobic silica, It it is generation to methyl using silicic acid anhydride by the way that surface to be had to the hydrophilic silicon oxides particle of hydrophilic silanol base The hydrophobic group substitution surface hydrophilic base of table, to manufacture.The organo-silicon compound used as silicic acid anhydride agent, have halosilanes, Hexamethyldisilazane, polysiloxane (polysiloxanes) etc., wherein, using facture it is simple, relative to wet type titanium dioxide Si hydrophobic excellent effect and it is most common, easy polysiloxanes is bought from market is favourable.If in this case, poly- silicon The viscosity of oxygen alkane is low, then molecular weight is also low, therefore the strand of the hydrophobic group imported shortens.On the other hand, it is wet The particle of formula silica, as the structure of its own, it is made up of the agglomerate of multiple minimum minuteness particles, therefore, The wet silicon dioxide particle itself, its internal micropore with the extremely majority for including air.Therefore, carried out at hydrophobization The hydrophobic silica particles of reason, made by the collaboration of the hydrophobic group substituted on surface and the air for bringing inside into With, and show hydrophobicity, even if using above-mentioned silicic acid anhydride, also will not the hydrophilic group on surface all taken by hydrophobic group Generation, the hydrophilic silanol base of remaining in the part on surface.Much less, hydrophobic of the remaining silanol base towards reduction particle surface Property direction effect.Under the premise of such, by using the hydrophobization being made up of the polysiloxanes that viscosity is more than 100cst Inorganic agent, the strand of hydrophobic group become longer, surface that can be by the strand effective over remaining silanol base.Therefore, The hydrophobization degree that hydrophobization wet silicon dioxide particle can be made is higher hydrophobization degree, can be under a small amount of coating weight Now effective anti-adhesion performance.When the viscosity of polysiloxanes is less than 100cst, the strand of hydrophobic group shortens, therefore can not the phase Treat above-mentioned effect.
Invented in ［ 2 ］（2nd invention）In, the formation of anti-adhesion layer on layer is sealed in heat-sealing, uses bigger hydrophobic of particle diameter Property wet silicon dioxide particle.Therefore, sealed in heat-sealing in the case that layer formed by hotmelt, even if the adhesive melts, With being compared using the situation of ultra tiny dry type silica, particle diameter is big, therefore above-mentioned particle is difficult to sink to heat-sealing and sealed in layer, no Its surface can significantly be reduced exposes area.Moreover, it can effectively prevent the reduction of the anti-adhesion performance caused by heat affecting. Although this is same with the first technology shown in above-mentioned patent document 2, in the present invention, and then above-mentioned hydrophobicity wet type two is used as Silicon oxide particle, wet silicon dioxide using especially height hydrophobization, specifically using being surface treated into two just The adsorbance of butylamine is below 200mmol/kg hydrophobization wet silicon dioxide particle.Such hydrophobic silica grain Son, the surface of its own have high hydrophobicity, therefore the anti-adhesion layer formed by the hydrophobicity wet silicon dioxide, than Excellent anti-adhesion performance is given full play under the coating weight of less silicon dioxide granule.It is additionally, since using few coating weight I.e. enough, therefore silicon dioxide granule can be kept to seal stationarity, the adherence of layer relative to heat-sealing well, can avoided close Put forth effort the coming off of the silicon dioxide granule caused by deficiency, peel off it is caused through when performance reduce, it is unhygienic.
Here, the di-n-butyl amine adsorbance of hydrophobic silica（Hereinafter referred to as " DBA adsorbances "）, turn into expression and dredge The index of the degree of aquation.That is, common silica, formed even with any preparation method of dry type preparation method and wet type preparation method , all there is the substantial amounts of silanol base as hydrophilic group in its surface.Di-n-butyl amine, reacted with silanol base, ions binding Ground is adsorbed on silicon dioxide granule.On the other hand, hydrophobic silica, can be by will have silanol base on surface originally Hydrophilic silicon oxides particle with silanes and/or it is polysiloxane-based carry out silicic acid anhydride, so as to methyl for representative Hydrophobic group substitutes surface hydrophilic base, thus manufactures.But it is not the whole of surface hydrophilic base even if silicic acid anhydride yet Substituted by hydrophobic group, inevitably the unreacted silanol base of remaining to a certain degree.Moreover, particularly wet silicon dioxide grain In the case of son, the particle structure of its own is made up of the agglomerate of more several minimum particulates, internally has majority The porous structure of micropore, therefore also remaining unreacted hydrophily silanol base internally.Therefore, it is hydrophobic by making to have carried out Change the silicon dioxide granule absorption di-n-butyl amine of processing, determine its adsorbance, be able to know that the hydrophobicity of silicon dioxide granule Degree.
In addition, hydrophobicity wet silicon dioxide particle, has with unreacted state remaining on surface and inside as described above Silanol base to a certain degree.Because the silanol base is hydrophily, therefore the affinity of the resin component melted to heating is poor, And then hinder the infiltration of the resin component.That is, the low-melting-point resin composition of layer is being sealed because of the high heat affecting applied during heat-sealing, heat-sealing When having melted, also function such that prevent its gap for hastily being penetrated between silicon dioxide granule by capillarity and The micropore of inside particles.It is therefore prevented that the hydrophobicity table caused by particle surface and internal voids are excessively covered by resin component The significantly attenuating in face, mitigate the performance degradation caused by heat affecting.I.e. it is capable to it is favorably improved the resistance to of anti-adhesion layer It is hot.
In ［ 3 ］ invention, there is composition and this two side of the composition of ［ 2 ］ invention of ［ 1 ］ invention, therefore be able to ensure that above-mentioned This two side of ［ 1 ］ and ［ 2 ］ effect.
As ［ 4 ］ invention, the viscosity for the above-mentioned polysiloxanes of silicic acid anhydride agent is preferably below 2000cst. When its more than 2000cst so as to it is too high when, instead cause surface hydrophobicity reduction tendency.It is considered that this is following reason institute Cause：The strand of hydrophobic group becomes a length of micropore for needing the above, covering the surface of silicon dioxide granule, it is impossible to brings air into In particle, as a result, the hydrophobic brought by air can not be given full play to and acted on.
In ［ 5 ］ invention, dimethyl polysiloxane is used by the polysiloxanes for being used as silicic acid anhydride agent, can be used It is most common, easily buy and cheap inorganic agent it is simple and effectively silicic acid anhydride to desired hydrophobization degree.
In ［ 6 ］ invention, use hydrophobicity wet type dioxy DBA adsorbances controlled in 30~100mmol/kg scope SiClx particle, therefore using the hydrophobicity of its own height having, surface hydrophobicity, it can realize more excellent anti-adhesion Performance and good adherence.
In ［ 7 ］ invention, by by the coating weight of hydrophobic silica particles（Adhesion amount）Set in terms of weight after drying It is set to 0.1~1.0g/m2, necessary and sufficient anti-adhesion performance can be assigned to anti-adhesion layer.
It it is 0.5~7.0 μm by being used as hydrophobicity wet silicon dioxide particle to use average grain diameter in ［ 8 ］ invention Hydrophobicity wet silicon dioxide particle, the good adherence that layer is sealed to heat-sealing is able to maintain that, and heat-sealing will not be damaged and seal layer Heat sealability, sealing intensity, container sealing property in terms of homogeneous and stable excellent performance can be presented.
In ［ 9 ］ invention, below anti-adhesion layer the heat-sealing of side seal layer, by containing ethene-beta-unsaturated esters copolymer, The wax and the resin combination of tackifier that fusing point is more than 80 DEG C are formed, wherein, it is more than 90 DEG C by using its softening point Resin combination, it is possible to increase the heat resistance of anti-adhesion layer, the heat endurance of its anti-adhesion performance is significantly increased, to container After main body seals use, can also remain above-mentioned well excellent prevents content adhesion effect.
The raising effect of such heat resistance, according to the investigation of the present inventor, it is believed that reached by following phenomenon 's.That is, the anti-content adhesion layer for sealing the outer surface for sealing layer is being arranged at by hydrophobicity wet silicon dioxide particle with adding In the relation that layer is formed, even if being filled out by heating during drying after the silicon dioxide granule dispersed liquid coating or content The hot shadow being directly subject to when the radiant heat from hot plate being subject in standby during container sealing after filling and heat-sealing from hot plate Ring etc., it can also suppress or prevent the low melting point composition early stage in resin combination and exceedingly melt and high fluidity is presented. That is, it is high by the softening point of resin combination, its melting delay can be made, additionally be able to suppress its melting.As a result, it can prevent Only：The hydrophobicity wet silicon dioxide particle of anti-adhesion layer inadvertently sinks to heat-sealing and sealed in layer, or being melt into for layer is sealed in heat-sealing The gap entered because of capillarity between silicon dioxide granule is divided to fill above-mentioned gap.It is therefore contemplated that it can prevent The only extreme reduction for exposing area of the hydrophobic surface of above-mentioned silicon dioxide granule, remaining good prevents content attachment effect Fruit.
In ［ 10 ］ invention, the softening point of resin combination is more than 100 DEG C, and the fusing point of wax is more than 90 DEG C, therefore Can more conscientiously and well obtain heat resistance improve effect.
In ［ 11 ］ invention, by being used as ethene-beta-unsaturated esters copolymer, fusing point is used as 75~100 DEG C of ethene-no Saturation ester copolymer, can ensure conscientiously good heat sealability, sealing, for breaking a seal when appropriate release performance it is same When, the anti-content adhesion property of excellent heat stability is ensured conscientiously.Beta-unsaturated esters list as ethene-beta-unsaturated esters copolymer Body, it is the second of esters of unsaturated carboxylic acids, the vinylacetate of methyl acrylate, ethyl acrylate, methyl methacrylate etc. etc Alkenyl esters etc..Preferably ethylene-vinyl acetate copolymer, ethylene methyl methacrylate copolymer.
In ［ 12 ］ invention, the ethene-no by ethene-beta-unsaturated esters copolymer using 70~100 DEG C of melting range Saturation ester copolymer, and wax seals the resin combination for sealing layer using the wax of the higher melt of 80~130 DEG C of fusing point by forming Softening point be set in 90~160 DEG C of scope, thus do not damage low temperature heat seal and synthetically can reach conscientiously above-mentioned ［ 9 ］ The various effects of~［ 11 ］ invention.
In ［ 13 ］ invention, by the resin combination for making composition heat-sealing seal layer there is ethene-beta-unsaturated esters copolymer to be The composition that 30~50 weight %, wax are 30~50 weight %, tackifier are 5~25 weight %, good heat sealability, close can be reached Feng Xing, for breaking a seal when appropriate release performance and prevent content adhesion effect heat endurance raising.
In ［ 14 ］ invention, because the oil absorption of hydrophobicity wet silicon dioxide particle is more than 50ml/100g, therefore When heat-sealing is sealed layer and melted, low melting point, the ability of low molecular weight compositions adsorbed contained by it to quick and substantial amount are excellent, can Sufficiently achieve the effect of heat resistance raising.The higher limit of oil absorption is not especially important in the present invention.For wet silicon dioxide 250~below the 350ml/100g of oil absorption having is i.e. enough, it is not necessary to which selection is used with the special of the oil absorption more than it Wet silicon dioxide.Reason be by cause cost improve bring it is unfavorable larger.
In ［ 15 ］ invention, seal layer by heat-sealing is using more than 90 DEG C of softening point, the melt viscosity at 160 DEG C Below 4000mPas resin combination, improves the heat resistance of anti-adhesion layer, and will seal the upper of the melt viscosity that seals layer Rise and be suppressed to relatively low, thus improve and be mingled with sealing, and the heat endurance of anti-adhesion performance can be significantly improved, to container master Body seal use after, can also remain above-mentioned well excellent prevents content adhesion effect.
The raising effect of the heat endurance of such anti-adhesion performance, according to the investigation of the present inventor, it is believed that be by such as Under phenomenon reach.That is, wet by hydrophobicity with the additional anti-content adhesion layer for being arranged at the outer surface that layer is sealed in heat-sealing In the relation that formula silicon dioxide granule layer is formed, though by during drying after the silicon dioxide granule dispersed liquid coating plus It is direct when the radiant heat from hot plate being subject in standby during container sealing after heat or Contents Fill and heat-sealing Heat affecting being subject to from hot plate etc., it can also suppress or prevent the low melting point composition early stage in resin combination and exceedingly melt And high fluidity is presented.That is, it is high by the softening point of resin combination, its melting delay can be made, additionally be able to suppress it molten Melt.As a result, it can prevent：The hydrophobicity wet silicon dioxide particle of anti-adhesion layer inadvertently sinks to heat-sealing and sealed in layer, or Heat-sealing seals gap that the molten component of layer enters because of capillarity between silicon dioxide granule to fill above-mentioned gap.Cause This, it is believed that the extreme reduction for exposing area of the hydrophobic surface of above-mentioned silicon dioxide granule can be prevented, remains good Prevent content adhesion effect.
It is that the heat-sealing of container body and cover piece is sealed between layer in addition, turning into for hydrophobicity wet silicon dioxide particle and being situated between Field trash, by improve heat-sealing seal the softening point of layer and the rising of melt viscosity is suppressed to it is relatively low, specifically, pass through by The melt viscosity at 160 DEG C of heat-sealing temperature is considered to suppress in below 4000mPas, after in heat-sealing, layer melting is sealed in heat-sealing, Hydrophobicity wet silicon dioxide particle easily and rapidly enters the heat-sealing and sealed in layer.I.e. it is easy to silicon dioxide granule is received Enter heat-sealing to seal in layer.Therefore, it is mingled with that sealing is excellent, less needs the temperature that improves when sealing and can seal.Namely Say, do not damage low temperature seal.And then thus can also play to greatest extent by make heat-sealing seal layer softening point be 90 DEG C The raising effect for the above-mentioned heat endurance brought above.
In ［ 16 ］ invention, ethene-beta-unsaturated esters copolymer uses ethene-unsaturation of 70~100 DEG C of melting range Ester copolymer, and wax and tackifier use softening point or the relatively high softening-point of 80~130 DEG C of fusing point or the material of fusing point, Thus the softening point for forming the resin combination that layer is sealed in heat-sealing is set in 90~160 DEG C of scope, and will be molten at 160 DEG C Melt-viscosity is set in 2000~4000mPas scope, so as to not damage low temperature heat seal and synthetically can reach conscientiously State the various effects of ［ 15 ］ invention.
In ［ 17 ］ invention, heat-sealing seals layer by containing acid modified polyolefin system resin, with wax and/or tackifier as required The resin combination of composition is formed, and the fusing point of above-mentioned wax and tackifier is all more than 80 DEG C, thus first certainly can be by leaps and bounds The adherence that hydrophobicity wet silicon dioxide particle seals layer with heat-sealing is improved, coming off, being partially stripped for anti-adhesion layer will not be produced, Not having the hydrophobicity wet silicon dioxide particle of anti-adhesion layer to be included into infringement in content prevents the anxiety of adhesion effect.Wax composition Much less, tackifier composition also has larger tribute in terms of the adherence of hydrophobicity wet silicon dioxide particle as described above is improved Offer.
In addition, the above-mentioned composition of layer is sealed in heat-sealing, the heat resistance of anti-adhesion layer can be improved, significantly improves its anti-adhesion performance Heat endurance, also remaining above-mentioned well after the heat-sealing to container body excellent prevents content adhesion effect.Heat The wax composition in layer is sealed, important effect is undertaken with the adherence of hydrophobicity wet silicon dioxide particle to improve, but with Problem in the heat endurance for prevent adhesion effect be present toward general used wax.On the other hand, the present invention's prevents adhesion effect Heat endurance, i.e. the raising effect of heat resistance, according to the investigation of the present inventor, it is believed that reached by following phenomenon 's.That is, the anti-content adhesion layer for sealing the outer surface for sealing layer is being arranged at by hydrophobicity wet silicon dioxide particle with adding In the relation that layer is formed, even if being filled out by heating during drying after the silicon dioxide granule dispersed liquid coating or content The hot shadow being directly subject to when the radiant heat from hot plate being subject in standby during container sealing after filling and heat-sealing from hot plate Ring etc., it can also suppress or prevent the low melting point composition early stage in resin combination and exceedingly melt and high fluidity is presented. That is, it is all high by the wax of resin combination and/or the fusing point of tackifier, it can postpone their melting, additionally be able to suppress Their melting.As a result, it can prevent：The hydrophobicity wet silicon dioxide particle of anti-adhesion layer inadvertently sinks to heat-sealing and seals layer In, or heat-sealing seals gap that the molten component of layer enters because of capillarity between silicon dioxide granule to fill above-mentioned Gap.It is therefore contemplated that the extreme reduction for exposing area of the hydrophobic surface of above-mentioned silicon dioxide granule can be prevented, maintain Good prevents content adhesion effect.
［ 18 ］ cover piece of invention, first, the anti-adhesion layer being made up of its hydrophobicity wet silicon dioxide particle, is by right Male and fomale(M＆F) of the entire surface of the outer surface of layer formed with highly less than 100 μm of most microspikes is sealed throughout heat-sealing, is assigned Hydrophobicity wet silicon dioxide particle is formed.Therefore, hydrophobicity wet silicon dioxide particle dispersion liquid coating work In sequence, flowing, liquid sagging on the face of dispersion liquid are prevented by above-mentioned microspike, it is equal to be able to easily form particle distribution Even anti-adhesion layer.That is, the excess electron excess fraction or extreme few on the contrary of hydrophobicity wet silicon dioxide particle can effectively be prevented Part etc. distribution it is inclined.Moreover, on this basis, by the adhesion amount of hydrophobicity wet silicon dioxide particle be set to Few 0.05g/m2More than, anti-adhesion layer can be made good to prevent content adhesion effect throughout comprehensively having.
Moreover, by the adhesion amount of the hydrophobicity wet silicon dioxide particle in anti-adhesion layer, it is set as at most thinly The amount below the degree of the top end face of highly low microspike as described above is covered, anti-adhesion layer, microspike be present Part heat-sealing expose with sealing layer point-like or the very thin part as hydrophobicity wet silicon dioxide particle layer, these parts exist Exist on face with point-like by close distribution.Therefore, in heat-sealing portion, hydrophobicity wet silicon dioxide particle layer, which turns into, to be mingled with Thing, heat sealability will not be significantly damaged, sealing intensity, sealing can be maintained well, and the sealing intensity time can be made And all-round ground is uniformly, and then the release performance of stabilization when can also improve Kaifeng.On the other hand, although anti-adhesion layer is by a small amount of Hydrophobicity wet silicon dioxide population form, but that such as distinguished by the contrast of embodiment described later and comparative example Sample, throughout the layer being universally distributed as hydrophobicity wet silicon dioxide uniform particle, therefore it is stable to present entire surface Necessary and sufficient degree prevent content adhesion effect.Moreover, the microspike existing for point-like in anti-adhesion layer, prevents Come off and peel off with unintentionally silicon dioxide granule in when only cover piece operates, and prevent due to the interference with outside The generation of albefaction trace caused by the friction of thing, while preventing content adhesion effect of stabilization is maintained long-term, in no way inferior Outward appearance maintenance on have contribution.
In ［ 19 ］ invention, the surface of anti-adhesion layer side is formed with the low-frictional force table of specific confficient of static friction Face, much less thus there is stable sliding, the extraction from platen roller（Feed）Property, the steady of cover piece can be carried out to heat-sealing portion Fixed smoothly feeding, the generation of the process disturbances caused by the supply mistake of cover plate can be reduced, before heat-sealing In a series of process, for the lid of the punching type used corresponding to the display printing punching of each cover plate for unit cover plate In the case of part, it will not also cause printing position with being punched the spacing deviation of position, the good unit lid that can be stablized The Blanking Shaping of piece.
Furthermore in this manual, softening point is to pass through ring and ball method（According to the JIS K6863 " softening points of hotmelt Test method "）Obtain, fusing point is by DSC methods（According to JIS K7121 " the transition temperature assay methods of plastics "）Obtain 's.
Brief description of the drawings
Fig. 1 is the sectional view for representing the summary that the lamination of the cover piece for preventing content from adhering to of the present invention is formed.
Embodiment
Fig. 1 represents the present invention（1st, 2 inventions）One of the lamination composition for the cover piece for preventing content from adhering to being related to.Should Cover piece, have by base material film layer（2）With metal foil layer（3）Lamination form substrate layer（1）, and in the substrate layer（1）Gold Belong to paper tinsel（3）The outer surface of side, apply when lid uses towards on the face of the side of the inside of container body across middle resin layer（4） And seal layer provided with heat-sealing（5）.Above-mentioned lamination is formed, same with the lamination of conventional cover piece, here, by substrate layer（1）/ middle Resin bed（4）Layer is sealed in/heat-sealing（5）Laminated body be referred to as " cover piece main body ".
The cover piece of the present invention for preventing content from adhering to, it is to seal layer in the heat-sealing of above-mentioned cover piece main body（4）Appearance Face also additionally has anti-adhesion layer（6）Cover piece.
Base material film layer（2）The table side of packing container is configured at, as its material, polyester, polyethylene, poly- third can be illustrated The individual layer or composite membrane of alkene, polyamide, polyacrylate, makrolon, polyvinyl chloride, cellulose ethanoate, glassine paper etc. or Laminated body that person forms these films, laminated resin in paper etc. etc..Base material film layer（2）Generally it is appropriately carried out printing（7）, carry out quilt Assign design.
Metal foil layer（3）The layer of barrier properties for gases, light-proofness etc. is to confer to, mostly using aluminium foil.Particularly drunk in coffee In the cover piece of the container of material and Yoghourt, as the metal foil layer for meeting light-proofness, light weight, preferably thickness 5~100 is used μm or so aluminium foil.In addition, with base material film layer（2）Lamination adhesive in general adhesive can be used.
Furthermore as substrate layer（1）, can also be without using metal foil layer（3）And use silica, aluminum oxide etc. Metal evaporation is in base material film layer（2）Metal deposition film.
Middle resin layer（4）, it is to be situated between to be substrate layer（1）Layer is sealed with heat-sealing（5）Between, defined rigidity is given to cover piece And/or the layer of resiliency during for sealing, suitably it is arranged as required to.Usually, the poly- second of 5~40 μm of thickness can be used Alkene, polypropylene, ethene-（Methyl）Acrylic copolymer, ethene-（Methyl）Olefin resin, the polyamides of acrylate copolymer etc. Amine, polyester, makrolon, polyvinyl chloride etc..
Layer is sealed in heat-sealing（5）As long as with intermediate layer resin layer（4）And the good layer of cementability of container side, then its material Material is not particularly limited, but particularly in the cover piece for paper/polyethylene can that Yoghourt etc. is packed for, it is generally preferable to use hot melt Adhesive.In addition, among hotmelt, it is desirable to use using wax and ethene-beta-unsaturated esters copolymer as principal component, its surplus For the tackifier of rosin etc., so be desirable for by containing more than 30 weight %, preferably comprise more than 40 weight % ethene-insatiable hunger The hotmelt formed with the thermoplastic resin group composition of ester copolymer such as ethylene-vinyl acetate copolymer.That is, ethene- In hotmelt of the amount of beta-unsaturated esters copolymer less than 30 weight %, as the wax of low melting point composition and containing for rosin The amount of having relatively increases, therefore according to experimental result, the tendency for reducing the heat resistance of anti-adhesion layer becomes strong.Its reason speculate be because For, because dry when and/or heat-sealing when by it is hot influenceed, above-mentioned low melting point components fuse, be adsorbed in hydrophobicity wet type dioxy Quantitative change on SiClx particle is more, and then reduces the hydrophobic surface product of the particle, it is possible to makes to prevent adhesion effect from reducing.
The thickness of layer is sealed on heat-sealing, is not particularly limited, but is considered from cost, sealing, productivity etc., typically It is set to 3~100 μm or so of thickness, preferably 10~50 μm of scope.
［ explanation of the anti-adhesion layer in the 1st invention ］
The anti-adhesion layer (6) of the main composition key element of the 1st invention is formed, it is characterized in that, using following wet silicon dioxides Particle is formed, and the wet silicon dioxide particle is：Make organo-silicon compound with synthesizing noncrystalline dioxy by damp process manufacture SiClx is the hydroxy chemical reaction on the surface of wet silicon dioxide particle, so as to impart hydrophobic hydrophobicity wet type titanium dioxide Silicon particle, and more than viscosity 100cst polysiloxanes has especially been subjected to silicic acid anhydride for inorganic agent.The present invention, The hydrophobicity wet type titanium dioxide of silicic acid anhydride has been carried out by using the polysiloxanes as use more than viscosity 100cst Silicon particle, using the teaching of the invention it is possible to provide the particle itself can be made to carry high hydrophobic, and then also with high under few coating weight The cover piece of anti-content tack.
Its reason is presumed as follows.
First, by using wet silicon dioxide particle, the particle is more in fabrication stage surface silanol groups, and then should In the case that surface has carried out silicic acid anhydride, compared with dry type silica, excellent hydrophobicity, hydrophobicity are typically shown. That is, with being dry type silica particle of the offspring as least unit using the agglomerate of the internal primary particle without pore Compare, not only particle diameter is big, and internally has the most micropores for including air, big relative to the specific surface area of particle diameter, Pore volume is also big.Therefore, the wet type particle being hydrophobic, by the effect of hydrophobic group that is substituted on surface with receiving Enter the synergy of the effect to the air of micropore, play excellent hydrophobicity, hydrophobicity.
In addition, in this 1st invention, as the silicic acid anhydride agent of wet silicon dioxide particle, especially using as Main framing has a polysiloxanes of the polymer of siloxanes key, and using using viscosity to enter for more than 100cst polysiloxanes Silicic acid anhydride is gone, thus, material has been formed as anti-adhesion layer, the more excellent material of performance can be turned into.
As the species of polysiloxanes, it is not particularly limited, such as can also uses hydrogenated methyl diene polysiloxanes, But easiness, cost from processing etc. consider, it is recommended to use dimethyl polysiloxane most typically.
Here, the reasons why viscosity of the polysiloxanes is set into more than 100cst, is the item tried to achieve from experimental result, make It is contemplated that for its mechanism as follows.
That is, wet silicon dioxide particle, it is not the complete of its surface in the case of having been handled by polysiloxane hydrophobic yet The hydrophilic group in portion（Silanol base）Substituted by hydrophobic group, a part of remaining silanol base on surface.The remaining silanol base is hydrophily, Therefore harmful effect is natively given to hydrophobicity, but in the case where the viscosity of polysiloxanes is set into more than 100cst, entered The strand of the hydrophobic group of row substitution is long in preferable scope, can cover remaining silicon by the strand with appropriate scope The surface of alcohol radical.Thus, it is possible to it is regarded to the hydrophobization Du Genggao for making the surface of wet silicon dioxide particle.In fact, work as When the viscosity of polysiloxanes is less than 100cst, it is impossible to obtain obtaining the hydrophobization effect of the degree sufficiently met.Estimate this It is because the strand of hydrophobic group substituted is short, therefore caused by not covering the surface of remaining silanol base fully.
But on the other hand, polysiloxanes viscosity more than 2000cst in the case of, instead show surface hydrophobic Property reduce tendency.It is considered that caused by this is following reason：The strand of hydrophobic group, which is crossed to grow to, needs the above, and it covers particle table The micropore in face, air can not be included by becoming particle, as a result, the hydrophobic effect brought by air can not give full play to.
From the point of view of as described above investigate, the viscosity for the polysiloxanes of hydrophobizers is necessarily more than 100cst, Preferably below 2000cst, more preferably 200~1000cst scope.
The particle diameter of the hydrophobicity wet silicon dioxide particle used in 1st invention, preferably using the μ of average grain diameter 0.5~7.0 The hydrophobicity wet silicon dioxide particle of m scope.
It is such few not had undesirable effect to heat sealability substantially when being less than 0.5 μm of particulate using average grain diameter Can not be accessed under coating weight, the scope of adhesion amount good prevents content adhesion effect.Use more than on the contrary 7.0 μm that During the thick particle of sample, the adherence that layer (5) is not only sealed with heat-sealing is deteriorated, and damages heat sealability.It is preferred that use average grain Footpath is the particulate of 2.0~5.0 μm of scope.
In addition, anti-adhesion layer（6）In above-mentioned hydrophobicity wet silicon dioxide particle adhesion amount（Coating weight）, set It is scheduled on 0.1~1.0g/m2Scope, be preferably set to 0.4~0.6g/m2Scope.When hydrophobicity wet silicon dioxide particle Adhesion amount is less than above-mentioned lower limit 0.1g/m2When, it is impossible to obtain good preventing content adhesion effect.And when adhesion amount surpasses Cross above-mentioned higher limit 1.0g/m2When, content adhesion effect saturation is prevented, on the other hand, anti-adhesion layer (6) infringement heat-sealing is sealed The heat sealability of layer (5), specifically, compared with the situation without anti-adhesion layer (6), sealing intensity（Peel resistant strength）Reduce More than 20%, the anxiety that the sealing for having stable good container is compromised.Moreover, layer is sealed with heat-sealing（5）Adherence Reduce.
［ explanation of the anti-adhesion layer in the 2nd invention ］
The anti-adhesion layer (6) of the main composition key element of the 2nd invention is formed, it is characterized in that, using following wet silicon dioxides Particle is formed, and the wet silicon dioxide particle is：Make organo-silicon compound with synthesizing noncrystalline dioxy by damp process manufacture SiClx is the hydroxy chemical reaction on the surface of wet silicon dioxide particle, so as to impart hydrophobic hydrophobicity wet type titanium dioxide Silicon particle, and especially highly silicic acid anhydride to cause DBA adsorbances（Di-n-butyl amine adsorbance）For Below 200mmol/kg.By the present invention in that the silicic acid anhydride as is hydrophobic below DBA adsorbances 200mmol/kg Property wet silicon dioxide particle, using the teaching of the invention it is possible to provide the particle itself carries high hydrophobicity, and then has under its few coating weight There is the cover piece of high anti-content adhesion property.
Its reason is presumed as follows.
First, by using wet silicon dioxide particle, the particle is more in fabrication stage surface silanol groups, and then should In the case that surface has carried out silicic acid anhydride, compared with dry type silica, excellent hydrophobicity, hydrophobicity are typically shown. That is, compared with the dry type silica particle of the agglomerate of the internal primary particle without pore, wet silicon dioxide grain Not only its particle diameter is big for son, and internally has the most micropores for including air, big relative to the specific surface area of particle diameter, carefully Pore volume is also big.Therefore, the wet silicon dioxide particle being hydrophobic, by the work of the hydrophobic group substituted on surface With the synergy of the effect of the air with bringing micropore into, excellent hydrophobicity, hydrophobicity are played.On this basis, exist In the present invention, by using so that its own display of wet silicon dioxide particle below DBA adsorbances 200mmol/kg value The hydrophobicity wet silicon dioxide particle that very hydrophobic has been handled, the higher hydrophobicity of display, play further excellent anti-attached Performance.
Here, in this 2nd invention, represent that the DBA adsorbances of the hydrophobic degree of wet silicon dioxide particle are advised It is come defined based on experimental result to be set to below 200mmol/kg.That is, 200mmol/kg DBA adsorbances are being used more than In the case of hydrophobicity wet silicon dioxide particle, anti-adhesion layer can not be made to play well anti-adhesion under few coating weight Performance.On the other hand, when making coating weight more for this, the adherence that silicon dioxide granule itself seals layer relative to heat-sealing is deteriorated, Produce the possibility increase that the particle of anti-adhesion layer comes off, is partially stripped.
But wet silicon dioxide particle, it is not surface even if implementing sufficient silicic acid anhydride as described above yet Hydrophilic group all substituted by hydrophobic group, the inevitably hydrophily silanol base of remaining to a certain degree.The remaining silanol base, Although being helpless to hydrophobicity, the hydrophily that has by it, poor to the affinity of molten resin composition, this is helped on the contrary In the heat-resistant stability for ensuring anti-adhesion layer.That is, when applying the pressure heat drying after being formed by anti-adhesion layer or heat-sealing When the high heat affecting that is subject to from thermal station, when low melting point components fuse, the liquidation of layer are sealed in heat-sealing, can also prevent to a certain degree Only：The gap to be formed because capillarity penetrates between the silicon dioxide granule of anti-adhesion layer such as above-mentioned molten resin composition and The reduction of anti-adhesion performance caused by the small internal voids of particle itself, the hydrophobic surface of covering particle, in the party Face is deemed helpful in heat resistance raising.From this point of view, DBA adsorbances, it is contemplated that with the difficulty in hydrophobic silica manufacture Relation in the case of, show more than 30mmol/kg value it is appropriate.Therefore, the preferable DBA of hydrophobicity wet silicon dioxide The scope of adsorbance is 30~100mmol/kg.
In addition, the particle diameter of the hydrophobicity wet silicon dioxide particle used in the 2nd invention, it is desirable to use average grain diameter is Less than 6.0 μm, the hydrophobicity wet silicon dioxide particle particularly preferably using average grain diameter for 0.2~5.0 μm of scope.
During using average grain diameter more than particle thick as 6.0 μm, the adherence that layer (5) is not only sealed with heat-sealing becomes Difference, and produce infringement heat sealability probably.On the other hand, when being used below 0.2 μm of small particle, substantially not to heat sealability Have undesirable effect such few coating weight, the scope of adhesion amount can not access good prevents content adhesion effect. It is preferred that the hydrophobicity wet silicon dioxide particle using the scope that average grain diameter is 2.0~5.0 μm.
In addition, anti-adhesion layer（6）In above-mentioned hydrophobicity wet silicon dioxide particle adhesion amount（Coating weight）, set It is scheduled on 0.1~1.0g/m2Scope, be preferably set to 0.2~0.5g/m2Scope.When hydrophobicity wet silicon dioxide particle Adhesion amount is less than above-mentioned lower limit 0.1g/m2When, it is impossible to obtain good preventing content adhesion effect.And when adhesion amount surpasses Cross above-mentioned higher limit 1.0g/m2When, content adhesion effect saturation is prevented, on the other hand, anti-adhesion layer (6) infringement heat-sealing is sealed The heat sealability of layer (5), specifically, compared with the situation without anti-adhesion layer (6), sealing intensity（Peel resistant strength）Reduce More than 20%, the anxiety that the sealing for having stable good container is compromised.Moreover, layer is sealed with heat-sealing（5）Adherence Reduce.
It is the common explanation of the 1st invention, the 2nd invention below.
In the present invention（1st, 2 inventions）In the manufacture for the cover piece being related to, anti-adhesion layer（6）Formation by the following method come Carry out：First, modulation has disperseed the dispersion liquid of hydrophobicity wet silicon dioxide particle with normal concentration in organic solvent, by it Layer is sealed in the heat-sealing being coated in cover piece main body（5）Outer surface.
For the solvent of the modulation of dispersion liquid, in order to ensure heat-sealing of the hydrophobicity wet silicon dioxide particle for substrate is sealed Layer（5）Stationarity, tack, preferably using organic solvent.Particularly preferably using the organic solvent with polar group.Its In, it is suitable using alcohols, particularly considers from cost, security, the presentation effect of hydrophobicity etc., use ethanol And/or methanol is appropriate.
The dispersion concentration of silicon dioxide granule in dispersion liquid, it is contemplated that with the relation of the coating weight of the particle and arbitrarily Setting, but less than 2%（Silicon dioxide granule 2g：Solvent 100ml）When, it is difficult to realize the uniform of an adequate amount of silicon dioxide granule Coating, when for high concentration more than 10% when, coating weight easily becomes superfluous.Suitable dispersion concentration substantially 3~6% or so.
The coating means of dispersion liquid, known arbitrary method can be used.For example, arbitrarily it can be coated with using gravure roll Method, injection coating, wire rod rubbing method etc..
The coating weight of dispersion liquid, much less, it should be and the hydrophobicity wet type titanium dioxide as described above in anti-adhesion layer (5) Coating weight corresponding to the adhesion amount of silicon particle.
Then, after above-mentioned working procedure of coating, by cover piece main body for drying process, wave the solvent in coating dispersion liquid Dissipate, form the desired anti-adhesion layer (6) of the hydrophobicity wet silicon dioxide uniform particle distribution of dry ormal weight.This is dry Dry can spontaneously dry, but seal layer with heat-sealing to improve operating efficiency and hydrophobicity wet silicon dioxide particle（5）It is close The property, preferably carried out by compulsory heat drying.Heating condition now is not particularly limited, but should be set as temperature 80 ~140 DEG C, preferably 100~120 DEG C, 5~30 seconds time, preferably 10~20 seconds or so.Temperature is less than above-mentioned lower limit 80 DEG C when, drying process spends the time, and when the time is less than 5 seconds, drying becomes insufficient, in operation behind, easily produces anti- The stripping of the part of adhesion layer, come off.And when drying temperature is set as into high temperature more than 140 DEG C or will be set the time When being set to the time more than 30 seconds, there are surface hydrophobic, hydrophobicity that hydrophobicity wet silicon dioxide particle has to be compromised it Anxiety.
［ explanation being suitably composed of layer is sealed in heat-sealing ］
In the present invention（1st, 2 inventions）In, seal layer as heat-sealing（5）, it is preferably following such composition.
Layer is sealed in heat-sealing（5）, with intermediate layer resin layer（4）And the cementability of container side must be good.Layer is sealed in above-mentioned heat-sealing （5）It is preferred that being made up of following resin combinations, the resin combination contains ethene-beta-unsaturated esters copolymer, wax and tackifier As required composition, also contain the additive of anti-blocking agent, antioxidant etc. as needed as any condition.
Resin combination using the composition seals layer as heat-sealing, and this is as in the past known but in the past general general The resin combination, as its must composition wax, used the wax compared with low melting point.For example, most typically use 65 DEG C of fusing point The paraffin of left and right, even the Tissuemat E of higher fusing point, used to the wax of 75 DEG C or so of high-melting-point.Moreover, Above-mentioned resin combination typically employed by the resin combination of 65 DEG C~90 DEG C or so of softening point.
In the present invention, the wax of one of required composition as above-mentioned resin combination, especially using 80 DEG C of fusing point with Wax that is upper, being preferably more than 90 DEG C, more preferably more than 100 DEG C, the softening point for making resin combination is more than 90 DEG C, excellent Elect more than 100 DEG C, more preferably more than 105 DEG C as.Softening point is set by the wax containing such higher melt Obtain higher resin combination and seal layer for heat-sealing, thus can significantly improve the outer surface side that layer is sealed in heat-sealing as described above The hydrophobicity for the anti-adhesion layer being additionally formed and the heat endurance for adhering to preventing property.
But the use of the too high wax of fusing point, can cause the viscosity of resin combination to uprise, there is processing adaptability to reduce it Anxiety, there is the anxiety that the good heat sealability of the stabilization of layer is sealed in infringement heat-sealing, therefore preferably using the wax below 130 DEG C of fusing point.It is more excellent Choosing is using the wax below 120 DEG C of fusing point, particularly preferably using the wax below 110 DEG C of fusing point.
In addition, the softening point of above-mentioned resin combination, fusing point or softening point are used by other compositions beyond wax High material, can also improve above-mentioned softening point, but by making the fusing point of wax with above-mentioned, by the softening point of resin combination It is set as more than 90 DEG C, can be most simple and effectively realizes desired effect.
Even if improve the softening point of resin combination, the wax of the high low melting point of mobility by improving the fusing point of resin Easily melt, enter between the hydrophobic particulate of anti-adhesion layer, make to prevent adhesion effect from reducing, therefore preventing adhesion effect Heat endurance on be difficult to expectation and have sufficient improvement.
In addition, the use of the too high resin combination of softening point, there is infringement heat-sealing to seal the machinability of layer and stable The anxiety of good heat sealability, therefore preferably using the resin combination below 160 DEG C of softening point.More preferably use softening point 140 Below DEG C, particularly preferably using less than 120 DEG C of resin combination.
Ethene-beta-unsaturated esters copolymer of the required composition of layer is sealed as heat-sealing, as its beta-unsaturated esters monomer, can be made With the vinyl esters of the esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, methyl methacrylate, vinylacetate etc Deng, wherein, particularly preferably using vinylacetate, methyl methacrylate.
In addition, above-mentioned ethene-beta-unsaturated esters copolymer, preferably using the ethene-insatiable hunger for the scope that fusing point is 70~100 DEG C And ester copolymer.When its fusing point is less than 70 DEG C, it is too low to seal the seal temperature of layer due to heat-sealing, therefore has preventing for anti-adhesion layer The anxiety of the heat endurance reduction of adhesion effect.On the contrary, when its fusing point is more than 100 DEG C, low temperature heat seal suffers damage, sealing Slow, operating efficiency when actual Contents Fill seals reduces.Most preferably fusing point is 75~95 DEG C of scope.
In addition, the wax as the required composition in resin combination, can enumerate paraffin, microwax, lignite wax, Fischer-Tropsch and close Into wax（Fischer-Tropsch wax）, Tissuemat E, polypropylene wax, Brazil wax, modified waxes etc., more preferably Tissuemat E.
In addition, as tackifier, rosin, rosin derivative can be enumerated（Hydrogenated rosin, rosin, rosin ester are not homogenized）, fat Ring family Petropols, fragrant family Petropols, Copolymer Petropols or their hydrogen addition product, terpene resin（α- Firpene, nopinene）Deng preferably using the hydrogen addition product of fragrant family Petropols, this is optimal.
In addition, the cooperation ratio of components of the required composition of resin combination is, it is necessary to consider softening point, melt viscosity, Low Temperature Thermal Feng Xing, heat seal strength, Kaifeng intensity etc. are set, by the way that ethene-beta-unsaturated esters copolymer is preferably set into 30~50 weights Amount %, be more preferably set as 35~45 weight %, wax be preferably set to 30~50 weight %, be more preferably set as 35~45 weight %, Tackifier are preferably set to 5~25 weight %, are more preferably set as 15~25 weight %, can reach good heat sealability, sealing Property, for breaking a seal when appropriate release performance and prevent content adhesion effect heat endurance raising.That is, ethene-no The use level of saturation ester copolymer is less than 30 weight % resin combination, cannot get sufficient sealing intensity, therefore not preferred. If conversely more than 50 weight %, sealing intensity is excessive, and the easily openable of closure suffers damage, therefore not preferred.In addition, wax Use level when being less than 30 weight %, the coating adaptability of thermoplastic resin composition（Process adaptability）Suffer damage, also, easily Kaifeng property suffers damage, therefore not preferred.On the other hand, when more than 50 weight %, it cannot get sufficient sealing intensity, therefore It is not preferred.In addition, tackifier, when its use level is less than 5 weight %, it is difficult to sufficient sealing intensity is obtained, conversely more than 25 weights Measure % and contain too much it is sometimes possible to the adhesion effect that prevents of anti-adhesion layer reduces, thus it is not preferred.
Embodiment
［ embodiment of the 1st invention ］
Then, the various experimental examples and its result for being shown as the 1st The effect of invention of confirmation and carrying out.
（The making of cover piece main body）
As base material film（2）, using 12 μm of polyethylene terephthalate film of thickness, in its one side, utilize poly- ammonia The aluminium foil of 30 μm of ester system dry lamination adhesive coating thickness（3）, be formed as substrate layer（1）.
Then, in above-mentioned substrate layer（1）Aluminium foil（3）The surface of side, utilize adhesive lamination adhesive similar to the above The polyethylene film that 20 μm of thickness, form middle resin layer（4）, and then on the outside of it, heat-sealing is formd using gravure roll rubbing method Seal layer（5）.With thus obtained substrate layer（1）/ middle resin layer（4）Layer is sealed in/heat-sealing（5）Laminated body as cover piece main body. Here, seal layer as above-mentioned heat-sealing（5）, using by the weight % of the ethylene-vinyl acetate copolymer 55/weight % of wax 40/tackifier （Rosin）The hotmelt that 5 weight % composition is formed, coating weight are set to 18g/m2。
（The formation of anti-adhesion layer）
As the hydrophilic wet silicon dioxide particle manufactured by damp process, the dioxy of 2.7 μm of average grain diameter has been used SiClx particle（Trade name " サ イ ロ ホ ー PVC ッ Network 200 "）.
On the other hand, as silicic acid anhydride agent, prepared viscosity be adjusted to respectively 50cst, 100cst, 200cst, 1000cst, 2000cst, 2500cst 6 kinds of dimethyl polysiloxanes.
Also, above-mentioned various dimethyl polysiloxane is used, by above-mentioned wet silicon dioxide particle respectively according to routine Method carries out silicic acid anhydride, and 6 kinds of hydrophobicity wet silicon dioxide particles corresponding with above-mentioned inorganic agent viscosity are made.
Then, by above-mentioned various hydrophobicity wet silicon dioxide particles, it is molten that ethanol is all scattered in 5% dispersion concentration In agent, various dispersion liquids are modulated, use gravure roll rubbing method by these various dispersion liquids with 0.1~1.0g/ as shown in table 1,2 The outer surfaces of layer (5) is sealed in the above-mentioned heat-sealing that the various coating weights of m2 scope are coated on cover piece main body, then force drying, is obtained Sealed in heat-sealing on layer (5) formed with the anti-content adhesion layer (6) being made up of above-mentioned hydrophobicity wet silicon dioxide particle Various samples.Furthermore the coating weight shown in table 1,2, all it is the weight for representing dried hydrophobicity wet silicon dioxide particle The coating weight of ratio.
（Evaluation test）
Then, following evaluation tests has been carried out to each sample.
（1）Anti-adhesion performance
To the back side of the cover piece of each sample, i.e. anti-adhesion layer outer surface on, the drop as about 0.5cc drips ア ロ エ ヨーグルト（Gloomy Yoghourt forever:Aloe Yoghurt）（MORINAGA MILK INDUSTRY Co., LTD.'s trade mark " the gloomy ロ of ア forever エ ヨ ー グ Le ト」）, above-mentioned drop " angle of inclination when starting to roll " when sample is gently tilted is determined, is sentenced by following benchmark to evaluate It is fixed.
◎ ● ● ● less than 15 degree
Zero ● ● ● less than more than 16 degree 30 degree
△ ● ● ● less than more than 31 degree 45 degree
× ● ● ● more than 46 degree
（2）Adherence
Vertically mounting is wound with the counterweight of black cloth on the face of the anti-adhesion layer of the cover piece of each sample（500g）, gently Length 200mm friction is carried out, visual inspection is attached to the silica volume of cloth.
Then, by the transfer adhesion amount of the hydrophobicity wet silicon dioxide on black cloth（Overburden amount）By following metewands Evaluation.
◎ ● ● ● do not adhere to substantially
Zero ● ● ● there is the attachment of a little for being confirmed to be in permissible range
△ ● ● ● there are some attachments
× ● ● ● there is obvious more attachment
It is above-mentioned（1）The result of anti-adhesion benchmark test be shown in table 1, it is above-mentioned（2）Adherence evaluation test knot Fruit is shown in table 2.
Table 1
Table 2
First, as shown in the result of the test of " the anti-adhesion performance " of table 1, the dimethyl using silicic acid anhydride agent is being used The viscosity of polysiloxanes is that 50cst, 2500cst silicic acid anhydride agent have carried out the hydrophobicity wet silicon dioxide grain of hydrophobization In the sample of son, the situation ratio with above-mentioned viscosity is 100cst, 200cst, 1000cst, 2000cst, anti-adhesion performance is confirmed It is all poor.For 50cst when, the tendency that anti-adhesion performance reduces is shown in the case of especially few coating weight, it is believed that this be by It is short in the strand of hydrophobic group, therefore can not fully cover the reason of remaining silanol base.On the other hand, it is 2500cst in viscosity When display that same tendency, it is believed that because, to the above is needed, it covers, blocks titanium dioxide for the molecular chain length of hydrophobic group The micropore on the surface of silicon particle, include reduction of the air to micropore, the hydrophobic of air act on impaired reason.Particularly hydrophobization When the viscosity of inorganic agent is near 200cst, most good result can obtain.
In addition, as shown in the result of the test of " adherence " of table 2, the hydrophobicity wet silicon dioxide particle in anti-adhesion layer Adherence, in the system of all coating weights, be substantially without attachment（Come off）Or the degree of some attachments can be seen, As its tendency, show that coating weight is fewer, then the higher tendency of adherence.Caused by the tendency can be speculated being following reason, i.e., As coating weight merely increases, the amount increase of the hydrophobicity wet silicon dioxide to come off.Thus distinguish, for wet type titanium dioxide The viscosity of the inorganic agent of the silicic acid anhydride of silicon, big influence is not given to adherence.
Results verification more than arrives, by using using more than viscosity 100cst's, preferably 200~2000cst The hydrophobicity wet silicon dioxide particle that polysiloxanes has carried out silicic acid anhydride forms anti-adhesion layer, can compare in coating weight 0.1 few~1.0g/m2Scope play sufficiently anti-adhesion performance and adherence, and then in 0.4~0.6g/m of coating weight2's Scope can obtain higher effect.
［ embodiment of the 2nd invention ］
Then, the various experimental examples and its result in order to confirm the 2nd The effect of invention and carry out are shown.（Cover piece main body Make）
Operated in the same manner as " making of cover piece main body " in the embodiment of above-mentioned 1st invention, obtain cover piece main body.
（The formation of anti-adhesion layer）
As the hydrophilic wet silicon dioxide particle manufactured by damp process, different following 3 kind of particle diameter are prepared.
1.7 μm of wet silicon dioxide A average grain diameters
2.7 μm of wet silicon dioxide B average grain diameters
6.7 μm of wet silicon dioxide C average grain diameters
Then, silicic acid anhydride agent uses dimethyl polysiloxane, above-mentioned wet silicon dioxide A, B, C is carried out hydrophobic Change is handled, on every kind of particle, the DBA adsorbances that are made as hydrophobicity index show 30mmol/kg, 100mmol/kg, The hydrophobicity wet silicon dioxide particle of each 4 kinds of 200mmol/kg, 250mmol/kg value.
Then, above-mentioned various hydrophobicity wet silicon dioxide particles are all scattered in alcohol solvent with 5% dispersion concentration In, modulate various dispersion liquids, using gravure roll rubbing method, by these various dispersion liquids with table 3,4 shown in 0.05~1.5g/m2 The various coating weights of scope be coated on the above-mentioned heat-sealing of cover piece main body and seal the outer surfaces of layer (5), then force drying, obtain Seal on layer (5) formed with the anti-content adhesion layer (6) being made up of above-mentioned hydrophobicity wet silicon dioxide particle in heat-sealing Various samples.Furthermore the coating weight shown in table 3,4, all it is the weight for representing dried hydrophobicity wet silicon dioxide particle The coating weight of ratio.
（Evaluation test）
Then, above-mentioned evaluation test is carried out for each sample, have rated as described above " anti-adhesion performance " and " close The property ".The result of anti-adhesion benchmark test is shown in table 3, and the result of adherence evaluation test is shown in table 4.
Table 3
Table 4
First, as shown in the result of the test of " the anti-adhesion performance " of table 3, it is hydrophobic that anti-adhesion layer forms materials'use expression Property degree DBA adsorbances be below 200mmol/kg hydrophobicity wet silicon dioxide sample in, in coating weight（Attachment Amount）For 0.1g/m2Excellent anti-adhesion performance is all given full play of in the case of above.It is 250mmol/kg in DBA adsorbances In the case of, even if making coating weight increase a lot, the anti-adhesion performance that meet can not be obtained.In addition, titanium dioxide silicon grain The size of the particle diameter of son, king-sized influence is not given on above-mentioned performance.
In addition, as shown in the result of the test of " adherence " of table 4, the hydrophobicity wet silicon dioxide particle in anti-adhesion layer Adherence, in all systems for having used the different hydrophobicity wet silicon dioxide of DBA adsorbances, show substantially and do not have There is attachment（Come off）Or the good adherence of the degree of some attachments can be seen.As its tendency, show that coating weight is got over Few, then the higher tendency of adherence, in addition, when the average grain diameter of silicon dioxide granule is too big, shows adherence reduction Tendency.Caused by the tendency can speculate and be following reason, i.e. as coating weight merely increases, in addition, as particle diameter is about super Cross 6.0 μm and become big, the amount increase of the hydrophobicity wet silicon dioxide to come off.Thus distinguish, the hydrophobicity of wet silicon dioxide The DBA adsorbances of wet silicon dioxide, big influence is not given to for adherence.
Result more than confirms, by using below DBA adsorbances 200mmol/kg, preferably 100mmol/ Below kg hydrophobicity wet silicon dioxide particle forms anti-adhesion layer, can be in 0.1 fewer~1.0g/m of coating weight2's Scope plays sufficiently anti-adhesion performance and adherence.
［ embodiment for being used for the effect that confirmation is brought using the composition of above-mentioned ［ 9 ］ invention ］
（The making of cover piece main body）
As base material film（2）, using 12 μm of polyethylene terephthalate film of thickness, in its one side, utilize poly- ammonia The aluminium foil of 30 μm of ester system dry lamination adhesive coating thickness（3）, be formed as substrate layer（1）.
Then, in above-mentioned substrate layer（1）Aluminium foil（3）The surface of side, using adhesive similar to the above, lamination adhesive The polyethylene film that 20 μm of thickness, form middle resin layer（4）, and then on the outside of it, heat-sealing is formd using gravure roll rubbing method Seal layer（5）.By thus obtained substrate layer（1）/ middle resin layer（4）Layer is sealed in/heat-sealing（5）Laminated body as cover piece main body.
Here, seal layer as above-mentioned heat-sealing（5）, the various cooperations shown in aftermentioned table 5 have been prepared using following materials Resin combination.
Wax（WX）
WX（I）：The Tissuemat E that 108 DEG C of fusing point
WX（II）：The Tissuemat E that 104 DEG C of fusing point
WX（III）：The Tissuemat E that 94 DEG C of fusing point
WX（IV）：The microcrystalline wax that 80 DEG C of fusing point
WX（V）：The paraffin that 75 DEG C of fusing point
WX（VI）：The paraffin that 67 DEG C of fusing point
Resin（EVA）
EVA（I）：Ethylene-vinyl acetate copolymer（Vinylacetate amount 26%）, 76 DEG C of fusing point
EVA（II）：Ethylene-vinyl acetate copolymer（Vinylacetate amount 20%）, 82 DEG C of fusing point
EVA（III）：Ethylene-vinyl acetate copolymer（Vinylacetate amount 5%）, 105 DEG C of fusing point
Tackifier（TF）
TF（I）Petroleum hydrogenated resin
TF（II）Rosin
Then, use gravure roll rubbing method by the thermoplastic resin composition of the various compositions shown in table 5 with coating weight 18g/m2Ratio coated on above-mentioned middle resin layer (4), form heat-sealing and seal layer（5）.（The formation of anti-adhesion layer）
As the material of anti-adhesion layer, following hydrophobic inorganic particulates and thermoplastic resin particle are prepared.
Hydrophobic inorganic particulate（SP）
SP（I）：Hydrophobicity dry type silica primary particle average grain diameter 7nm
SP（II）：Hydrophobicity wet silicon dioxide average grain diameter 2700nm
SP（III）：Hydrophobicity wet silicon dioxide average grain diameter 3900nm
Thermoplastic resin particle（MP）
MP（I）：Ethylene-vinyl acetate copolymer（Vinylacetate 20%, ethene 80%, average grain diameter 100nm）
MP（II）：Vinyl acetate-vinyl chloride copolymer（Vinylacetate 20%, vinyl chloride 80%, average grain diameter 100nm）
By above-mentioned each hydrophobic inorganic particulate（SP）Or hydrophobic inorganic particulate（SP）With thermoplasticity particulate（MP）This two side It is dispersed in ethanol, has made coating fluid.The use level or thermoplasticity particulate and hydrophobic inorganic of hydrophobic inorganic particulate The mixing ratio of particulate is shown in table 5.
Then, by these various coating fluids, cover piece main body is coated on using gravure roll rubbing method（1）Above-mentioned heat-sealing seal layer （5）Outer surface, and force drying forms anti-adhesion layer.Furthermore coating weight, set in sample No.1~14 and 17~21 It is set to 0.5g/m2（Weight after drying）, it is set as 0.8g/m in sample No.15,162（Weight after drying）.In addition, force dry It is dry all to be carried out under the drying condition of 15 seconds 100 DEG C × time of temperature.
（Make the species of sample）
Among the sample 1~21 of various cover pieces as obtained from above-mentioned shown in table 5, sample 1~9,19 is to change heat Seal the sample that the wax in layer, resin, softening point investigate its influence.Sample 10 is to change the sample that tackifier investigate its influence. Sample 11~14,20~21 is that the mixing ratio for changing each composition that layer is sealed in heat-sealing investigates its sample influenceed.Sample 15,16 is It is the layer being made up of the mixture of hydrophobic inorganic particulate and thermoplasticity particulate to make anti-adhesion layer, and coating weight is changed into 0.8g/m2Investigate the sample of its influence.Sample 17,18 is that the particle diameter for changing hydrophobic inorganic particulate investigates its sample influenceed.
（Evaluation test）
（1）Anti-adhesion performance
To the back side of the cover piece of each sample No.1~21, i.e. anti-adhesion layer outer surface on, as about 0.5cc drop drip Lower ア ロ エ ヨ ー グ Le ト（MORINAGA MILK INDUSTRY Co., LTD.'s trade mark " the gloomy ロ of ア forever エ ヨ ー グ Le ト "）, determine sample slowly Ground above-mentioned drop " angle of inclination when starting to roll " when tilting, is judged to evaluate by following benchmark.
◎ ● ● ● less than 15 degree
Zero ● ● ● less than more than 16 degree 30 degree
× ● ● ● more than 31 degree
（2）Anti-adhesion performance after heat treatment
For each cover piece of each sample No.1~21, the 1st heat resistant test is the fire-bar of " 30 seconds 100 DEG C × time of temperature " Part, the 2nd heat resistant test are the heating condition of " the 100 DEG C × time of temperature 10 divides ", and the 3rd heat resistant test is the " 100 DEG C × time of temperature 15 points " heating condition, for being cooled to each sample of normal temperature after each sample is taken care of in heating atmosphere respectively, carried out with It is above-mentioned（1）Same anti-adhesion benchmark test.
（3）Sealing
（Seal intensity and Kaifeng intensity）
The cover piece of sample No.1~21 is heat sealed to container body with the air-proof condition of 150 DEG C × 90kgf × 1.0 second（Paper/ Polyethylene container）Flange surface on.
Also, " sealing intensity " is according to province order of the Japan on the ingredient standard of breast and dairy products etc.（54 year April 16 of Showa Day Health and human services department makes No. 17）Strength test method of sealing be measured, seal be determined as when intensity is more than 13.3kPa it is qualified （◎ symbols）, less than 13.3kPa when be determined as it is unqualified（× symbol）.
Then, " Kaifeng intensity ", it is that cover piece is pulled with 45 ° of the elevation angle, 100mm/ point speed, maximum when breaking a seal is carried Lotus is as Kaifeng intensity（N）.Moreover, the scope of optimal Kaifeng intensity is defined as 8~15N, by Kaifeng intensity in the scope It is qualified that interior sample is evaluated as（◎ symbols）, the sample outside the scope be evaluated as it is unqualified（× symbol）.
（Heat seal strength）
The cover piece of sample No.1~21 cuts into 15mm is wide, is sealed with the air-proof condition of 150 DEG C × 0.2MPa × 1.0 second To container body（Paper/polyethylene container）On the pane wide 15mm that cuts.Then, by direction of the cover piece at 180 ° On pulled with 100mm/ point speed, using maximum load when peeling off as heat seal strength.
Moreover, the heat seal strength by the cover piece for the cover piece subjective situation for being not provided with anti-adhesion layer（The resistance to stripping of cover piece is strong Spend sealing）As a reference value, judge to evaluate the reduced rate or increment rate of heat seal strength by following benchmark.
◎ ● ● ● intensity decreases or increase are less than 10%
Zero ● ● ● intensity decreases increase as 10% less than 20%
× ● ● ● intensity decreases increase as more than 20%
（4）Adherence
Vertical mounting is wound with the counterweight of black cloth on the face of the anti-adhesion layer of each cover piece of sample No.1~21（500g）, Length 200mm friction is gently carried out, visual inspection whether there is the particulate for being attached to cloth surface.
Then, according to the hydrophobic particulate on black cloth and the transfer adhesion amount of thermoplastic resin particle（Overburden amount）, press The metewand stated is evaluated.
◎ ● ● ● do not adhere to substantially
Zero ● ● ● there is the attachment of a little for being confirmed to be in permissible range
× ● ● ● there is obvious more attachment
It is above-mentioned（1）~（4）The result of each evaluation test be shown in table 6.
As shown in the result of the test of " the anti-adhesion performance " of table 6, the present invention prevent content adhere to cover piece in, only It is that sample is slightly tilted into Yoghourt drop to begin to roll movement.Moreover, this prevents adhesion effect, it is such as " anti-attached after heat treatment Performance " the result finding of experiment, it is being subjected to 100 DEG C × 10 minutes and is being subjected to 100 DEG C × 15 minutes quite harsh Hot resume after, also do not reduce substantially, and maintained well.This shows：It is being filled with comprising Yoghourt, pudding, fruit After cover piece has been sealed in heat-sealing on the container of the content of the sticky liquid component of son jelly etc., for the content, prevent that this is interior The excellent effect of the tolerant attachment on the cover piece back side.Moreover, as shown in the result that " sealing " is tested, pass through anti-adhesion layer In the presence of sealing intensity, heat sealability（Sealing intensity）With easily openable all without there is big infringement, appropriate sealing is able to maintain that And assign above-mentioned anti-adhesion performance.Moreover, such as the result finding of " adherence " experiment, hydrophobic inorganic particles and contain it Anti-adhesion layer adherence it is good, without unintentionally hydrophobic inorganic particulate etc. separation come off, the part of anti-adhesion layer shell From the worry waited, it can chronically stablize and maintain anti-content adhesion property, and the sorrow that also no foreign matter is mixed into container.
The application be with Japan's patent application Patent 2012-171372 filed in August in 2012 1 day and The application of the priority request of Japan's patent application Patent 2012-171378, above-mentioned application filed in August in 2012 1 day Disclosure form the part of the application as former state.
Term as used herein and explanation, used to illustrate embodiments of the present invention, the present invention not by It is limited.The present invention, as long as in the range of patent protection is asked, then it can allow to appoint under limit without departing from its spirit What design alteration.
Description of reference numerals
1 ... substrate layer
2 ... base material film layers
3 ... metal foil layers
4 ... middle resin layers
Layer is sealed in 5 ... heat-sealings
6 ... anti-adhesion layers

Claims (18)

1. a kind of cover piece for preventing content from adhering to, being that at least there is substrate layer and heat-sealing to seal layer, and the outer of layer is sealed in the heat-sealing Surface is provided with the heat-sealing cover piece of anti-adhesion layer, it is characterised in that the anti-adhesion layer is by the poly- silicon using more than viscosity 100cst The hydrophobicity wet silicon dioxide particle that oxygen alkane has carried out silicic acid anhydride is formed.
2. the cover piece according to claim 1 for preventing content from adhering to, the two of the hydrophobicity wet silicon dioxide particle N-butylamine adsorbance is below 200mmol/kg.
3. the cover piece according to claim 1 or 2 for preventing content from adhering to, the poly- silica for silicic acid anhydride agent The viscosity of alkane is below 2000cst.
4. the cover piece according to claim 1 or 2 for preventing content from adhering to, the poly- silica for silicic acid anhydride agent Alkane is dimethyl polysiloxane.
5. the cover piece according to claim 2 for preventing content from adhering to, the two of the hydrophobicity wet silicon dioxide particle N-butylamine adsorbance is 30~100mmol/kg.
6. the cover piece according to claim 1 or 2 for preventing content from adhering to, the hydrophobicity wet type two in the anti-adhesion layer The coating weight of silicon oxide particle, 0.1~1.0g/m is calculated as with weight after drying2。
7. the cover piece according to claim 1 or 2 for preventing content from adhering to, the hydrophobicity wet silicon dioxide particle Average grain diameter is 0.5~7.0 μm.
8. the cover piece according to claim 1 or 2 for preventing content from adhering to, the heat-sealing seal layer by containing ethene-insatiable hunger Formed with the resin combination of ester copolymer, wax and tackifier as required composition, the softening point of the resin combination is 90 More than DEG C, and the fusing point of the wax is more than 80 DEG C.
9. the cover piece according to claim 8 for preventing content from adhering to, the softening point of the resin combination for 100 DEG C with On, and the fusing point of the wax is more than 90 DEG C.
10. the cover piece according to claim 8 for preventing content from adhering to, the fusing point of the ethene-beta-unsaturated esters copolymer For 70~100 DEG C.
11. the cover piece according to claim 1 or 2 for preventing content from adhering to,
The heat-sealing seals layer by containing resin combination of ethene-beta-unsaturated esters copolymer, wax and the tackifier as required composition Form,
The fusing point of the ethene-beta-unsaturated esters copolymer is 70~100 DEG C,
The fusing point of the wax is 80~130 DEG C,
The softening point of the resin combination is set to 90~160 DEG C.
12. the cover piece according to claim 8 for preventing content from adhering to, it is characterised in that the resin combination has The ethene-beta-unsaturated esters copolymer is 30~50 weight %, wax is 30~50 weight %, tackifier are 5~25 weight % Composition.
13. the cover piece according to claim 1 or 2 for preventing content from adhering to, the hydrophobicity wet silicon dioxide particle Oil absorption be more than 50ml/100g.
14. the cover piece according to claim 1 or 2 for preventing content from adhering to, the heat-sealing seal layer by 90 DEG C of softening point with The resin combination that melt viscosities upper, at 160 DEG C are below 4000mPas is formed.
15. the cover piece according to claim 1 or 2 for preventing content from adhering to,
The heat-sealing seals layer by containing resin combination of ethene-beta-unsaturated esters copolymer, wax and the tackifier as required composition Form,
The fusing point of the ethene-beta-unsaturated esters copolymer is 70~100 DEG C,
The softening point or fusing point of the wax and tackifier are 80~130 DEG C,
The softening point of the resin combination is 90~160 DEG C, and the melt viscosity at 160 DEG C is 2000~4000mPas.
16. the cover piece according to claim 1 or 2 for preventing content from adhering to,
The heat-sealing seals layer by containing the resin group of acid modified polyolefin system resin and wax and/or tackifier as required composition Compound is formed,
The fusing point of the wax and tackifier is all more than 80 DEG C.
17. the cover piece according to claim 1 or 2 for preventing content from adhering to,
The outer surface of layer is sealed in described seal, throughout entire surface the close multiple microspikes for being provided with less than 100 μm of height,
In the outer surface with the projection, formed with the anti-adhesion layer,
The anti-adhesion layer, its adhesion amount are set to 0.05g/m2At most cover above and somewhat the top of the microspike Below the amount in face.
18. the cover piece according to claim 1 or 2 for preventing content from adhering to, the quiet of surface of the anti-adhesion layer side rub Wipe coefficient and be set to less than 0.65.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926268A (en) * 2004-03-02 2007-03-07 旭化成纤维株式会社 Polyurethane elastic fiber and method for production thereof
CN101070439A (en) * 2007-06-12 2007-11-14 武汉理工大学 Method for preparing hydrophobic silicon dioxide

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2939292A1 (en) 1979-09-28 1981-04-09 Boehringer Mannheim Gmbh, 6800 Mannheim N-PHENOXYALKYLPIPERIDINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF, AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS
FR2563845B1 (en) 1984-05-03 1986-10-03 Pechiney Aluminium METHOD AND DEVICE FOR AUTOMATIC OVER-SUCTION ON ELECTROLYSIS TANKS FOR THE PRODUCTION OF ALUMINUM
JP3203292B2 (en) * 1994-08-08 2001-08-27 日本シリカ工業株式会社 Reinforcing filler for silicone rubber
DE10138490A1 (en) * 2001-08-04 2003-02-13 Degussa Hydrophobic precipitated silica with a high degree of whiteness and extremely low moisture absorption
CN100556963C (en) * 2007-07-12 2009-11-04 武汉理工大学 The preparation method of polymer coated silica composite particle
JP4668352B1 (en) * 2010-07-07 2011-04-13 昭和電工パッケージング株式会社 Contents adhesion prevention lid material and manufacturing method thereof
JP5670690B2 (en) * 2010-10-06 2015-02-18 昭和電工パッケージング株式会社 Contents adhesion prevention lid material and manufacturing method thereof
JP5102871B2 (en) * 2010-12-24 2012-12-19 昭和電工パッケージング株式会社 Content adhesion prevention lid
JP5722639B2 (en) * 2011-01-12 2015-05-27 昭和電工パッケージング株式会社 Content adhesion prevention lid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926268A (en) * 2004-03-02 2007-03-07 旭化成纤维株式会社 Polyurethane elastic fiber and method for production thereof
CN101070439A (en) * 2007-06-12 2007-11-14 武汉理工大学 Method for preparing hydrophobic silicon dioxide

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